US3037010A - Polymeric perfluoro-2-butyne - Google Patents
Polymeric perfluoro-2-butyne Download PDFInfo
- Publication number
- US3037010A US3037010A US699184A US69918457A US3037010A US 3037010 A US3037010 A US 3037010A US 699184 A US699184 A US 699184A US 69918457 A US69918457 A US 69918457A US 3037010 A US3037010 A US 3037010A
- Authority
- US
- United States
- Prior art keywords
- radiation
- butyne
- perfluoro
- energy
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WBCLXFIDEDJGCC-UHFFFAOYSA-N hexafluoro-2-butyne Chemical compound FC(F)(F)C#CC(F)(F)F WBCLXFIDEDJGCC-UHFFFAOYSA-N 0.000 title claims description 3
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 230000005855 radiation Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 5
- 230000005670 electromagnetic radiation Effects 0.000 description 4
- 230000005865 ionizing radiation Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000012857 radioactive material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- TXGPGHBYAPBDAG-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-4,4-bis(trifluoromethyl)cyclobutane Chemical compound FC(F)(F)C1(C(F)(F)F)C(F)(F)C(F)(F)C1(F)F TXGPGHBYAPBDAG-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
Definitions
- the polymers of this invention are obtained by exposing the bis-perfluoro-Z-butyne to ionizing radiation having an energy of at least 50 electron volts.
- the energy characteristics of one form of ionizing radiation can be expressed in terms which are appropriate for another form.
- radiation consisting of particles or photons having an energy of 0.1 mev. and over is preferred.
- polymerization of the bis-perlluoro-Z-butyne can be obtained with a minimum length of exposure to the radiation.
- Particles or photons with an energy equivalent of 0.5-4 mev. are the most useful from a practical standpoint. Radiation with higher energies (i.e., 1O mev. and higher) may also be employed.
- a minimum exposure of at least 0.01 watt-sec./cm. at the surface is necessary since lower degrees of exposure do not give practical quantities of product. Exposures as high as 10,000 to 100,000 watt-sec./cm. may be employed. The exposure may be carried out in one slow pass, or in several faster ones and may be conducted at any convenient rate of energy input.
- Suitable ionizing radiations for use in this invention include both radiation in the form sometimes regarded as particle radiation and radiation in the form sometimes regarded as ionizing electromagnetic radiation.
- particle radiation is meant an emission of accelerated electrons or nuclear particles such as protons, neutrons, a-particles, deuterons, El-particles, or the like, so that the said particle impinges upon the bis-perfluoro-Z- butyne.
- the charged particles may be accelerated by means of a suitable voltage gradient, using such devices as a cathode ray tube, resonant cavity accelerator, a Van de Graaff accelerator, a Cockcroft-Walton accelerator, or the like, as is well known to those skilled in the art.
- Neutron radiation may be produced by suitable nuclear reactions, e.g., bombardment of a beryllium target with deuterons or rat-particles.
- particle radiation suitable for carrying out the process of the invention may be obtained from an atomic pile, or from radioactive isotopes or from other natural or artificial radioactive materials.
- ionizing electromagnetic radiation radiation of the type produced when a metal target (e.g., tungsten) is bombarded by electrons possessing appropriate energy. Such radiation is conventionally termed X-ray.
- ionizing electromagnetic radiation suitable for carrying out the process of the invention may be obtained from a nuclear reaction (pile) or from natural or artificial radioactive material. In all of these latter cases the radiation is conventionally termed gamma rays.
- the bis-perfluoro-Z-butyne from which the polymers of this invention are made may be prepared by the method disclosed in US. Patent 2,546,997, issued April 3, 1951, to C. I. Glouchener.
- the charged reactor was then exposed to four passes, each of 1.1 seconds duration, under a 500 watt beam of 2 mev. electrons from a Van de Graaff generator.
- the absorption of electronic energy by the perfluoro-2butyne during this time was about 965 watt-sec.
- Films from the above polymer which are clear are obtained by pressing at 20,000 lbs./ sq. in. at ordinary room temperature (ca. 22 C.). These films, because of their transparency, combined with exceptional oxidative resistance and thermal stability, are useful as windows for high temperature equipment.
- Suitable media are hydrocarbons, especially fluorinated hydrocarbons, such as perfiuorodimethylcyclohexane, perfluorodimethylcyclobutane, etc. i
- reaction medium is not critical. A convenient amount will be about 1 to 1 weight ratio.
- the polymers of this invention are insoluble in the common organic solvent and when heated at temperatures at which they begin to decompose show no evidence of melting. As indicated in the example, however, they can be coalesced and shaped into useful articles.
- a pressure coalescible solid homopolymer of perfiuorQZ-butyne said polymer being stable at a temperature of 450 C. and not meltable without decomposition.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
United States Patent 3,037,010 POLYMERIC PERFLUORO-Z-BUTYNE John Ferguson Harris, Jr., Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Nov. 27, 1957, Ser. No. 699,184 2 Claims. (Cl. 260-921) This invention relates to new fluorine-containing polymers and to their preparation.
The discovery of polytetrafluoroethylene with its remarkable properties, particularly its high melting point, thermal stability, and chemical inertness, has given great impetus to the chemistry of the polyfluorinated unsaturated organic compounds. The fluorinated alkenes and alkanes have been studied extensively and much has been learned of the effect of the fluorine function in these compounds. Comparatively little, however, has been done with the fluorinated alkynes.
In accordance with the present invention, it has now been discovered that useful pressure-'coalescible polymers which are essentially insoluble and infusible can be prepared by subjecting bis-perfluoro-Z-butyne to high energy radiation. These polymers are further characterized by being stable at temperatures of at least 450 C., resistant to boiling nitric acid, and pressure-coalescible.
The polymers of this invention are obtained by exposing the bis-perfluoro-Z-butyne to ionizing radiation having an energy of at least 50 electron volts.
It is recognized that the energy characteristics of one form of ionizing radiation can be expressed in terms which are appropriate for another form. Thus, one may express the energy of either the particles of radiation commonly considered as particle radiation or of the photons of radiation commonly considered as wave or electromagnetic radiation in electron volts (ev.) or million electron volts (mev.). In the irradiation process of this invention, radiation consisting of particles or photons having an energy of 0.1 mev. and over is preferred. With radiation of this type, polymerization of the bis-perlluoro-Z-butyne can be obtained with a minimum length of exposure to the radiation. Particles or photons with an energy equivalent of 0.5-4 mev. are the most useful from a practical standpoint. Radiation with higher energies (i.e., 1O mev. and higher) may also be employed.
A minimum exposure of at least 0.01 watt-sec./cm. at the surface is necessary since lower degrees of exposure do not give practical quantities of product. Exposures as high as 10,000 to 100,000 watt-sec./cm. may be employed. The exposure may be carried out in one slow pass, or in several faster ones and may be conducted at any convenient rate of energy input.
Suitable ionizing radiations for use in this invention include both radiation in the form sometimes regarded as particle radiation and radiation in the form sometimes regarded as ionizing electromagnetic radiation.
By particle radiation is meant an emission of accelerated electrons or nuclear particles such as protons, neutrons, a-particles, deuterons, El-particles, or the like, so that the said particle impinges upon the bis-perfluoro-Z- butyne. The charged particles may be accelerated by means of a suitable voltage gradient, using such devices as a cathode ray tube, resonant cavity accelerator, a Van de Graaff accelerator, a Cockcroft-Walton accelerator, or the like, as is well known to those skilled in the art. Neutron radiation may be produced by suitable nuclear reactions, e.g., bombardment of a beryllium target with deuterons or rat-particles. In addition particle radiation suitable for carrying out the process of the invention may be obtained from an atomic pile, or from radioactive isotopes or from other natural or artificial radioactive materials.
nice
By ionizing electromagnetic radiation is meant radiation of the type produced when a metal target (e.g., tungsten) is bombarded by electrons possessing appropriate energy. Such radiation is conventionally termed X-ray. In addition to X-rays produced as indicated above, ionizing electromagnetic radiation suitable for carrying out the process of the invention may be obtained from a nuclear reaction (pile) or from natural or artificial radioactive material. In all of these latter cases the radiation is conventionally termed gamma rays.
The bis-perfluoro-Z-butyne from which the polymers of this invention are made may be prepared by the method disclosed in US. Patent 2,546,997, issued April 3, 1951, to C. I. Glouchener.
The example which follows illustrates the above method for preparing the polymers of this invention:
A rectangular aluminum dish, 11.3 cm. x 5.6 cm. x 4.4 cm., cooled in an acetone-solid carbon dioxide mixture, and covered with a polyethylene terephthalate film, was charged with 25 g. of perfluoro-Z-butyne. The charged reactor was then exposed to four passes, each of 1.1 seconds duration, under a 500 watt beam of 2 mev. electrons from a Van de Graaff generator. The absorption of electronic energy by the perfluoro-2butyne during this time was about 965 watt-sec. After the distillation of the unpolymerized perfluoro-Z-butyne, there was obtained 6.0 g. of a white, opaque, rather brittle, porous polymer in one piece, 0.23 cm. thick.
Examination of transparent films of this polymer show strong absorption bands in the region of 240 mu. This is indicative that the polymer has as the unit structure the grouping The polymer produced as above is extremely resistant to oxidation and shows remarkable thermal stability. Thus, refluxing for three days in concentrated nitric acid brings about only a 0.7% weight loss and heat treatment at 260 C. at 0.1 mm pressure for three days causes a weight loss of 0.7%. At 465 to 475 C. and atmospheric pressure the weight loss in three hours is 31%. In contrast to this figure a high molecular weight polytetrafiuoroethylene loses 66% in weight under the same conditions.
The above polymer when subjected to pressures of the order of 50,000 lb./ sq. in. at ordinary room temperature (ca. 22 C.) in a die yields chips which have the shape of the die and which are hard and transparent.
Films from the above polymer which are clear are obtained by pressing at 20,000 lbs./ sq. in. at ordinary room temperature (ca. 22 C.). These films, because of their transparency, combined with exceptional oxidative resistance and thermal stability, are useful as windows for high temperature equipment.
Although in the example the polymerization has been carried out in the absence of a reaction medium, it is to be understood that polymerization can be effected in the presence of an inert liquid medium. Suitable media are hydrocarbons, especially fluorinated hydrocarbons, such as perfiuorodimethylcyclohexane, perfluorodimethylcyclobutane, etc. i
The amount of reaction medium is not critical. A convenient amount will be about 1 to 1 weight ratio.
The polymers of this invention are insoluble in the common organic solvent and when heated at temperatures at which they begin to decompose show no evidence of melting. As indicated in the example, however, they can be coalesced and shaped into useful articles.
The outstanding resistance to oxidation and exceptional thermal stability of the polyperfluoroalkylacetylenes of this invention makes them uniquely useful in all applications where products possessing such properties are known to be useful, namely, as coatings for surfaces which are in contact with corrosive liquids, such as acids and bases, 5 as high temperature electrical insulation, etc.
I claim:
1. A pressure coalescible solid homopolymer of perfiuorQZ-butyne, said polymer being stable at a temperature of 450 C. and not meltable without decomposition. 10
2. The product of claim 1 in film form.
UNITED STATES PATENTS Rerny June 6, Gochenour Apr. 3, Lontz Apr. 22, Ruh et a1 Mar. 29, Miller Ian. 3, Tarrant et a1 June 12, Lewis et a1 Sept. 18, Bolstad et a1. Dec. 27,
Claims (1)
1. A PRESSURE COALESCIBLE SOLID HOMOPOLYMER OF PERFLUORO-2-BUTYNE, SAID POLYMER BEING STABLE AT A TEMPERATURE OF 450*C. AND NOT MELTABLE WITHOUT DECOMPOSITION
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US699184A US3037010A (en) | 1957-11-27 | 1957-11-27 | Polymeric perfluoro-2-butyne |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US699184A US3037010A (en) | 1957-11-27 | 1957-11-27 | Polymeric perfluoro-2-butyne |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3037010A true US3037010A (en) | 1962-05-29 |
Family
ID=24808288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US699184A Expired - Lifetime US3037010A (en) | 1957-11-27 | 1957-11-27 | Polymeric perfluoro-2-butyne |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3037010A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3211637A (en) * | 1962-08-31 | 1965-10-12 | Leo A Wall | Homopolymers of 4-chloroperfluoro-heptadiene-1, 6 |
| US3214358A (en) * | 1965-10-26 | Isobutylene-diene copglymerization by low temperature irradiatiun | ||
| US3684786A (en) * | 1971-11-26 | 1972-08-15 | Allied Chem | Process for preparing perfluoro-2-butyne polymer |
| US3772011A (en) * | 1971-11-04 | 1973-11-13 | Eastman Kodak Co | Print-out elements and methods using photoconductors and polygnes |
| US10887613B2 (en) | 2015-02-19 | 2021-01-05 | Magic Pony Technology Limited | Visual processing using sub-pixel convolutions |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2350330A (en) * | 1938-09-28 | 1944-06-06 | Theron P Remy | Treatment of hydrocarbons with radioactive materials |
| US2546997A (en) * | 1947-09-05 | 1951-04-03 | Hooker Electrochemical Co | Perfluoro carbon compounds |
| US2593583A (en) * | 1951-03-14 | 1952-04-22 | Du Pont | Method for coagulating aqueous dispersions of polytetrafluoroethylene |
| US2705229A (en) * | 1953-11-18 | 1955-03-29 | Dow Chemical Co | Preparation of octafluorohexatriene |
| US2729613A (en) * | 1951-02-19 | 1956-01-03 | William T Miller | Solid polymers of perhalogenated polyolefins |
| US2750431A (en) * | 1953-05-18 | 1956-06-12 | Tarrant Paul | 1, 1, 3-trifluorobutadiene, its polymer, and processes of making them and other 1, 1-difluorinated dienes and their polymers |
| US2763609A (en) * | 1952-06-03 | 1956-09-18 | Gen Electric | Vulcanization of silicone rubber with high energy electrons |
| US2966482A (en) * | 1956-03-01 | 1960-12-27 | Minnesota Mining & Mfg | Polymers of perfluorobutyne-2 |
-
1957
- 1957-11-27 US US699184A patent/US3037010A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2350330A (en) * | 1938-09-28 | 1944-06-06 | Theron P Remy | Treatment of hydrocarbons with radioactive materials |
| US2546997A (en) * | 1947-09-05 | 1951-04-03 | Hooker Electrochemical Co | Perfluoro carbon compounds |
| US2729613A (en) * | 1951-02-19 | 1956-01-03 | William T Miller | Solid polymers of perhalogenated polyolefins |
| US2593583A (en) * | 1951-03-14 | 1952-04-22 | Du Pont | Method for coagulating aqueous dispersions of polytetrafluoroethylene |
| US2763609A (en) * | 1952-06-03 | 1956-09-18 | Gen Electric | Vulcanization of silicone rubber with high energy electrons |
| US2750431A (en) * | 1953-05-18 | 1956-06-12 | Tarrant Paul | 1, 1, 3-trifluorobutadiene, its polymer, and processes of making them and other 1, 1-difluorinated dienes and their polymers |
| US2705229A (en) * | 1953-11-18 | 1955-03-29 | Dow Chemical Co | Preparation of octafluorohexatriene |
| US2966482A (en) * | 1956-03-01 | 1960-12-27 | Minnesota Mining & Mfg | Polymers of perfluorobutyne-2 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3214358A (en) * | 1965-10-26 | Isobutylene-diene copglymerization by low temperature irradiatiun | ||
| US3211637A (en) * | 1962-08-31 | 1965-10-12 | Leo A Wall | Homopolymers of 4-chloroperfluoro-heptadiene-1, 6 |
| US3772011A (en) * | 1971-11-04 | 1973-11-13 | Eastman Kodak Co | Print-out elements and methods using photoconductors and polygnes |
| US3684786A (en) * | 1971-11-26 | 1972-08-15 | Allied Chem | Process for preparing perfluoro-2-butyne polymer |
| US10887613B2 (en) | 2015-02-19 | 2021-01-05 | Magic Pony Technology Limited | Visual processing using sub-pixel convolutions |
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